Process of imparting hydrophobic properties to cellulose fibers



Patenteci Aug. 20, 1940 PROCESS OF IMPARTING HYDROPHOBI PROPERTIES T0CELLULOSE FIBERS Franz Emil Hubert, Dessau, Erwin Heisenberg, Leip g",and Adolf Steindorlf and Ludwig- Orthner, Frankfort-on-the-Main,Germany, assignors, by mesne assignments, to General Aniline & FilmCorporation, New York, N. Y., a corporation of Delaware No Drawing.Application September 28, 1937,

' Serial NO- 166324. In Germany May 11, 1935 8 Claims.

The present invention relates to a process of imparting hydrophobicproperties to cellulose fibers.

This application is a continuation-in-part of "our co-pending U. S.patentapplication Serial No. 81,122, filed May 21, 1936.

It is known that fibers of cellulose or hydrated cellulose, such ascotton, artlficialsilk or staple fiber are extraordinarily hydrophil,that is to say they are very quickly wetted when in' contact with water.This property is a great disadvantage for many 01' the applications ofthis material.

This invention consists in a process for making cellulose fibershydrophobe by applying to the fibers or incorporating with them acompound which contains at least one aliphatic or cycloaliphatic residuehaving at least 4 carbon atoms and capable of reacting :with aldehydeand exposing the fibers thus treated simultaneously or subsequently tothe action of an aliphatic aldehyde or dialdehyde, for instance,formaldehyde or glyoxal. v

Suitable compounds are, for example, fatty amines and fatty acid amidessuch as dodecyl- "amine, hexadecylamine octadecylamine,octadecenylamine, the amides of carboxylic acids, for example, abieticacid amide, lauric acid amide, stearic acid methylamide, stearic acidbutylamide, stearic acid octadecylamide, stearic acid amide, montanicacid amide, paraffin carboxylic acid amide, dichlorostearic acid amide,phenyl-' stearic acid amide, furthermore alkylbenzoic acid amides andthe nuclear hydrogenation products thereof, for instance,p-dodecylbenzoic acid amide and dodecylcyclohexylcarboxylic acidyIphenox-ypropionic acid amide; further compounds of the character ofalkyl-substituted ureas such as mono-isobutyl 'urea, monododecyl urea,mono-octadecyl urea, stearoyl urea; further fatty acid imlno ethers oramidines.

There also come into consideration compoundsv containing hydroxylgroups, such as, for instance,

dodecylphenol, di-isohexyl-phenol.

Instead of the products named above there may also be used withadvantage their products of reaction with aliphatic aldehydes, forexample, their methylol compounds. If these latter are used the separateafter-treatment with formaldehyde can be omitted in many cases, a simpleafter-heating operation suflicing.

The reaction products of carboxylic acid amides with formaldehyde, forinstance, have the general formula:

member of the group consisting of hydrogen and aliphatic hydrocarbonradicals.

The process may be conducted, for example, as follows: the cellulosefibers are first saturated with a solution of the aliphatic compound inan organic solvent, for instance, pyridine, acetone or in an aqueousemulsion ofthe aliphatic compounds. They are then dried and exposedto'the action of, for instance, formaldehyde. The formaldehyde may beadded to the impregnatingsolu ,tion so that a subsequent treatment withformaldehyde becomes unnecessary. 'In this case the fiber needs onlysubsequent heating to ensure sufilcient reaction of the formaldehydewith the impregnating compound and the fiber.

In many cases the ,hydrophobe effect is essentially enhanced if theimpregnation is carried out in the presence of an agent having a feeblyacid action, for example, acetic acid, lactic acid or agents of acidreaction such as sodium bisulfite. The impregnation may be carried outin an aqueous medium as well as in an organic solvent, such as benzine,carbontetrachloride, pyridine and the like. An agent having a feeblyacid action may be added during the impregnation, or it may beincorporated with the fiber by a preor' after-treatment.

Fibers treated in this manner are characterized by a particularly highstability towards water and even hot soap solution. For example, suchmaterial can be subjected to the usual fulling treatment, that is to sayheating for hour in a solution of 50 grams of soap and grams of sodiumcarbonate per liter at 50 C. without loss of the property of repellingwater. By suitable combination of the parent material and workingconditions an effect can be obtained which is not notably diminished byseveral washings with boiling soap solution.

An alternative method of incorporating the material in the fibersconsists in adding the compound in question as such or its condensationproduct with aldehyde to the spinning solution which is to serve as theparent material for making artificial cellulose threads. The fibersproduced from solutions containing such an addition may, if desired, besubsequently treated with an aliphatic aldehyde.

The following examples serve to illustrate the invention, but they-arenot intended to limit it thereto, the parts being by weight:

(1) Unsoaped, dry viscose silk is immersed for 5 minutes in 5 times itsweight of a solution of 5 to per cent. strength of methylol-stearinamidein pyridine. The goods are centrifuged. dried and heated for hours at110 C.

(2) Dry viscose artificial silk is treated for 15 minutes with asolution of 5 grams of a condensation product, obtainable from stearicacid amide and aqueous formaldehyde, in one liter of carbontetrachloride. The material is squeezed and dried at the air. Tbereuponit is after-treated at room temperature for 15 minutes with a solutionof 5 grams of lactic acid in 1 liter of water,

squeezed, dried in a current of air and heated for 2 hours at 110 C. Thematerial is finally well rinsed and dried.

(3) Non-dyed or dyed viscose artificial silk is treated with asolution-which contains per liter,

of water 5 grams of lactic acid or glycolic acid;

" erties to cellulose-fibers by impregnating the fibers in a bath whichcontains an N-methylol and is then dried. This pre-treated material istreated for 10 minutes at 60 C. to 70 C. with a solution of acondensation product, obtainable from montanic acid amide and aqueousformaldehyde, in carbon tetrachloride. The material is squeezed,dried'and heated for some minutes at a temperature of 140 C.Thereisfthus obtained a hydrophobe tissue having .a,very goodwater-repellant effect. l

(4) A cotton fabric is treated for a short time with an aqueous lacticacid solution of 1 per cent. strength and then dried at 50 C. to 60 C.It is subsequently impregnated for 10 minutes with a solution of 1 percent. strength of 9.10-dichlorostearic acid methylolamide incyclohexane, centrifuged and heated at 135 C. to 140 C. for minutes. I

(5) Artificial silk crepe is impregnated with an alcoholic solution of 2per cent. strength of dodecylbenzoic acid methylolamide. It is thensiueezed, dried at C. and heated for 1 hour at 1 0 C.

(6) Artificial silk crepe is treated for some minutes in an aqueousemulsion of p-dodecylphenylbutyric acid methylolamide, containing perliter 10 grams of the methylolamide and 5 grams of lactic acid. It issubsequently squeezed, dried at 50 C. to C. and heated for 30 minutes at130 C. to 140 C.

(7) Cotton calico isimpregnated for a short time with a solution of 2per cent. strength of the condensation product ofdodecylcycloli'exylbutyric acid amide and formaldehyde in carbontetrachloride. Then it is squeezed and heated for 1 hour at 140 C.

(8) Dyed artificial silk is impregnated with an alcoholic solutioncontaining'per liter 5 grams of.

m'aleic acid and 20 grams of isooctylphenoxyacetic acid methylol amide.After centrifuging the whole is heated for 1 hour at C. to C.

(9) 15 grams of beta-naphthoxyacetic acidmethylolamide are dissolved in1000 grams of alcohol and 10 grams of lactic acid are added to thissolution. Artificial silk fabric is treated in the bath so preparedfor,5 hour at 60 C. to 70 C. Then it is squeezed, dried at about 50 C. andsubsequently exposed to a temperature of C. for 60 minutes in a dryingcylinder or in a tentering frame or in a drying oven. The fabric hasbecome hydrophobe. The effect is enhanced by washing the fabric in asoap solution rendered alkaline by means of sodium carbonate andsubsequent drying.

,With a still better success there may be used a bath prepared in ananalogous manner and containing 10-15 grams ofiso-octyl-beta-naphthoxyacetic acid-methylolamide.

advisable.

We claim:

1. The process of imparting hydrophobic properties to cellulose fibersby incorporating with them an N-methylol compound of 'an acid amide of amonocarboxylic acid and ammonia which contains at least one radical withat least 4 carbon atoms selected from the group consisting of aliphaticand cycloaliphatic radicals and subsequently heating them.

2. The process of imparting hydrophobic propcompound of an acid amide ofa monocarboxylic acid and ammonia having at least one radical with atleast 4 carbon atoms selected from the group consisting of aliphatic andcycioaliphatic radicals and heating them after the impregnation.

, 3. The process of imparting hydrophobic properties to cellulose fibersby impregnating the fibers in a bath. which contains an N-methylolcompound of an acid amideof a monocarboxylic acid and ammonia having atleast one radical with at least 4 carbon atoms selected from the groupconsisting of aliphatic and cycloaliphatic radicals, and an agent ofacid action such as a feeble acid, and heating them after theimpregnation.

4. The process of imparting hydrophobic prop- .erties to cellulosefibers by impregnating the :the group consisting of aliphatic andcycloaliphat-ic radicals, in the presence of an age t of acid actionsuch as a feeble acid and heating them after the impregnation.

6. The process of imparting hydrophobic propleast 4 carbon atoms, in thepresence of a. feeble erties to cellulose fibers by impregnating thefibers acid and heating them after the impregnation. with a. compound ofthe general formula: "I. Waterproof cellulose fibers obtained by theprocess defined in claim 1. 8. Waterproof cellulose fibers obtained bythe 5 process defined in claim 6. FRANZ EMIL HUBERT.

cmon ERWIN HEISENBERG.

ADOLF STEINDORFE. 1 wherein R stands for an aliphatic radical with atLUDWIG'ORTHNER. 10

